JP2007224237A - Fluorescent coloring agent and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorescent coloring agent having high fluorescence exceeding the absorbency of black color, various excellent properties including fastness and capable of forming a record readable with ultraviolet ray. <P>SOLUTION: The fluorescent coloring agent contains a colored fluorescent pigment, a colored non-fluorescent pigment and a resin and has black hue. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a black fluorescent colorant.

  Conventionally, it has been impossible to read, discriminate and measure recorded information recorded with a black or gray pigment recording agent with ultraviolet rays. As a method for enabling such reading, a method in which a fluorescent dye is mixed with the recording agent can be considered.

  In the above method, when a fluorescent dye is mixed with a black or gray recording agent, if the amount of the fluorescent dye is small, the fluorescence emitted from the fluorescent dye is absorbed by the black dye even when the ultraviolet ray is irradiated. Cannot be detected. Further, even when a large amount of fluorescent dye is mixed, the phenomenon of concentration quenching of the fluorescent dye occurs, and thus it is impossible to emit fluorescence exceeding the light absorbency of the pigment used in combination. Furthermore, since fluorescent dyes generally have low light resistance, it has been difficult to construct a recording agent that can perform sufficiently reliable recording.

  Accordingly, an object of the present invention is to provide a fluorescent colorant having high fluorescence exceeding the absorbance due to black, excellent in various properties including fastness, and capable of recording that can be read by ultraviolet rays.

ただし、アゾ系など他の構造を持つ有彩色蛍光顔料や蛍光染料を体質顔料に染め付けたタイプの色素でも差し支えない。 The above problems are solved by the present invention described below. That is, the present invention provides a fluorescent colorant comprising a chromatic fluorescent pigment, a non-fluorescent chromatic pigment and a resin, and having a hue of black. An example of the chromatic fluorescent pigment is a chromatic fluorescent pigment represented by the following general formula (1). In the present invention, black includes gray.

However, chromatic fluorescent pigments or other dyes having other structures such as azo-based dyes may be used.

  In the present invention, the particle diameter of the chromatic fluorescent pigment is 0.03 to 10.0 μm; the blending mass ratio of the chromatic fluorescent pigment (A) and the non-fluorescent chromatic pigment (B) is 1 1 to 50: 1; the resin is poly (meth) acrylic resin, polyvinyl resin, polymaleic acid resin, polyester resin, polyether resin, polyurethane resin, polyamide resin, polyepoxy resin A resin and / or oligomer selected from a resin, a polycarbonate resin, a polysiloxane resin, a polyolefin resin, and a polyfunctional unsaturated bond-containing oligomer (ultraviolet ray / electron beam curable monomer) is preferable.

  The colorant of the present invention is useful as a colorant for stationery, a colorant for paint, a colorant for printing ink, a colorant for thermal transfer, a colorant for electrophotography, a colorant for inkjet ink, or a colorant for printing agent. . In addition, information can be recorded by using the fluorescent colorant by a coating method, a printing method, an ink jet method, a thermal transfer method, or an electrophotographic method.

  As a result of intensive studies, the present inventors have solved the defects of conventional fluorescent dyes, and while being crystalline fine particles like pigments, the hue is clear and emits strong fluorescence, and has coloring power as a pigment, The chromatic fluorescent pigment of the general formula (1) having sufficiently high concealability is represented by a non-fluorescent chromatic pigment, for example, blue such as copper phthalocyanine, green such as copper phthalocyanine green, or dioxazine violet. It has been found that when the color is adjusted to black by mixing with a purple pigment, the fluorescent color is emitted by overcoming the light absorption of the non-fluorescent chromatic pigment.

  Conventional dye-based fluorescent pigments cannot be used at high concentrations because they cause concentration quenching. In addition, since conventional dye-based fluorescent dyes generally have low light resistance, the fluorescence intensity becomes weak when exposed to light for a long period of time, and recording reliability is poor. In addition, since conventional dye-based fluorescent pigments have insufficient solvent resistance, recording is impaired when the recording medium is contaminated with a solvent. In contrast, the black fluorescent colorant according to the present invention is capable of emitting fluorescence under ultraviolet rays while being black, and has high light resistance, so that it is sufficiently reliable as an information recording agent. I have.

  In addition, when electrophotographic copying a recorded material using the colorant of the present invention, it is difficult to distinguish between the copy source and the copy under visible light, but the copy source emits strong fluorescence under ultraviolet light. Since the copy does not emit fluorescence, it is possible to easily distinguish between the two.

  Furthermore, the fluorescent pigment used in the present invention has the same hiding property as a normal pigment, and the colorant containing the fluorescent pigment is excellent in water resistance and solvent resistance, and is very strong in light resistance. It can withstand use. In addition, it is possible to impart washing resistance to the colored product by selecting a binder resin, and it is possible to record not only on paper and the like but also on fibers and the like.

ただし、アゾ系など他の構造を持つ有彩色蛍光顔料や蛍光染料を体質顔料に染め付けたタイプの色素でも差し支えない。 Next, the present invention will be described in more detail with reference to preferred embodiments. An example of a chromatic fluorescent pigment that is one component that is used in the present invention and mainly characterizes the present invention is a pyrazine fluorescent pigment represented by the general formula (1).

However, chromatic fluorescent pigments or other dyes having other structures such as azo-based dyes may be used.

  The chromatic fluorescent pigment represented by the general formula (1) used in the present invention is 2,5-dicyano-3,6-described in JP-A-5-32640 and JP-A-11-138974. It is a compound having diamino-pyrazine as a basic skeleton, and includes crystal modifications thereof. By introducing various substituents into the amino group, the hue can be changed to lemon yellow, yellow, orange or red.

Examples of the alkyl group having 1 to 6 carbon atoms in the substituents R _{1 to} R ₄ in the general formula (1) include an ethyl group, an n-propylene group, an isopropylene group, an n-butyl group, and sec-butyl. Group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group and the like, and carbon Examples of the alkenyl group having 2 to 6 include vinyl group, 2-propenyl group, allyl group, crotyl group, 1-butenyl group, 2-butenyl group, and bradienyl group.

  In addition, these alkyl groups and alkenyl groups may have an aryl group such as a phenyl group, a naphthyl group, an anthryl group, or a phenanthryl group as a substituent. Furthermore, these aryl groups may have 1 to 5 substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; An alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; It is done.

  These compounds can be synthesized by the method described in JP-A-5-32640, and specific examples include the compounds described in Table 1 below.

  The chromatic fluorescent pigment is obtained by heating and stirring a dye obtained by combining and reacting an appropriate intermediate compound with a suitable solvent to improve the purity and adjusting the crystal form. is there. It is also possible to make particles having relatively large crystallinity by heating with an appropriate solvent, and then to obtain the desired particle size using a grinding device. After synthesizing these chromatic fluorescent pigments, they are heated with a solvent to form crystals larger than the target particle size, and then wet-grinding using a grinding machine such as a ball mill, motor mill or dyno mill, and pigments and inorganic salts. It is also possible to use the mixture after adjusting the mixture to the desired particle size by dry grinding or the like using a ball mill or a kneader. The preferable particle diameter of the fluorescent pigment is 0.03 to 10.0 μm. When the particle size is too small, the concealability is lowered, while when the particle size is too large, the coloring power is lowered. Fine-graining of the fluorescent pigment may be performed before the fluorescent pigment is used as the colorant of the present invention, or may be performed at the time of producing the colorant of the present invention.

  As another non-fluorescent chromatic pigment that characterizes the present invention, a conventionally known pigment can be used. In addition to copper phthalocyanine (CI Pigment Blue 15) as a blue pigment, Metal phthalocyanine, low halogenated phthalocyanine having 1 to 4 halogen atoms, indanthrene blue (CI Pigment Blue 22), C.I. I. Bat Blue 4, 6, 20 and the like are C.I. I. Pigment Green 1, 2, 7, 7, 10, 12, 12, 36, 37, 38, C.I. I. Bat Green 1, C.I. I. Ingrain Green 3 is dioxazine violet (CI Pigment Violet 23) and C.I. I. Pigment violet 19, C.I. I. Pigment red 122, C.I. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 5, C.I. I. Bat Violet 1, C.I. I. Bat Violet 2, C.I. I. Bat Violet 3, C.I. I. Bat violet 10 or the like can be used. Furthermore, when adjusting the black color using the chromatic fluorescent pigment and the non-fluorescent chromatic pigment, if necessary, it is also possible to use a conventionally known pigment of another hue, for example, yellow or red. is there.

  The colorant of the present invention uses the chromatic fluorescent pigment described above as a fluorescent component, and adjusts to black by mixing a conventionally known non-fluorescent chromatic pigment. Regarding the constituent mass ratio of the non-fluorescent chromatic pigment (B), A: B is 1: 1 to 50: 1, and preferably 2: 1 to 20: 1. However, there is a significant difference in coloring power, that is, light absorption, depending on the type and nature of the non-fluorescent chromatic pigment used, while chromatic fluorescent pigment also has a difference in fluorescence emission ability depending on the type. Since the hue and the required fluorescence intensity also differ depending on each other, the composition ratio cannot be defined unconditionally and is not necessarily limited to the above range.

  The resin used in the fluorescent colorant of the present invention functions as a pigment dispersant or dispersion aid while the fluorescent colorant is in a liquid state, and is actually used as a recording agent. After printing on the recording medium and fixing to the recording medium, it functions as a fixing binder for the colorant.

  Resins used for such purposes include those commonly used in various paints, printing inks, stationery, inkjet inks or printing agents, as well as dry developers such as electrophotography, electrostatic printing or electrostatic recording. In addition, any resin used in wet developers, thermal transfer ink ribbons, films, etc. may be used, but in the case of the present invention, it is a resin that is not colored so as not to reduce the fluorescence intensity. It is also desirable that the resin absorb as little light as possible in the ultraviolet region.

  Preferred resins under such conditions include poly (meth) acrylic resins, polyvinyl resins, polymaleic acid resins, polyester resins, polyether resins, polyurethane resins, polyamide resins, polyepoxy resins, Examples thereof include resins and / or oligomers such as polycarbonate resins, polysiloxane resins, polyolefin resins, and polyfunctional unsaturated bond-containing oligomers (ultraviolet ray / electron beam curable monomers).

  As the above resin, conventionally known resins are used and are not particularly limited. Specifically, poly (meth) acrylic acid ester copolymer, poly (meth) acrylic acid- (meth) acrylic acid ester copolymer A poly (meth) acrylic resin such as poly (meth) acrylic acid-styrene- (meth) acrylic acid ester; a polyvinyl resin such as polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl chloride; a styrene-maleic acid copolymer; Examples thereof include maleic resins such as rosin-modified maleic acid; copolymers of the above (meth) acrylic acid monomers and other vinyl monomers.

  Also, polyester resins such as polyester resins obtained by ester condensation of dibasic acids such as succinic acid and sebacic acid and diols such as ethylene glycol and cyclohexanedimethanol, and alkyd resins containing long chain fatty acids; ethylene oxide And polyether resins such as polyethylene glycol, polyethylene glycol monoalkyl ether and polytetramethylene glycol, which are ring-opening polymers of tetrahydrofuran.

  Polyurethanes such as polyester polyurethane resins, polyether polyurethane resins and polysiloxane polyurethane resins which are urethane reaction products of diol components such as polyester, ethylene glycol and polysiloxane diol with diisocyanates such as isophorone diisocyanate and, if necessary, diamine. Based resins.

  Further, examples thereof include ring-opening polymers such as ε-caprolactam, and polyamide resins such as nylon 6 obtained by condensation of diamine and dibasic acid and polyamide resin of dimer acid / ethylenediamine of oleic acid.

  Polycarbonate resin such as polyhexyl carbonate; Polyepoxy resin; Polysiloxane resin; Polyolefin resin such as polyethylene, polypropylene and polyethylene vinyl acetate; Multifunctional unsaturated bond such as urethane acrylate and trimethylolpropane triacrylate Resins and / or oligomers such as containing oligomers (ultraviolet ray / electron beam curable monomers) are used. These can be used individually or in mixture of 2 or more types. Although content in the fluorescent colorant of the said resin is not specifically limited, Although it changes with kinds of fluorescent colorant, it is the range which occupies 0.1-50 mass% of a fluorescent colorant normally.

  In particular, in the present invention, since there is a demand for a resin that absorbs as little light as possible in the ultraviolet region and does not cause coloration, the resin skeleton has few aromatic rings and unsaturated bonds that have a structure with large absorption in the ultraviolet region. Or the resin which does not contain is preferable. However, in order to maintain the dispersibility of the colorant and the physical properties of the resin, an aromatic ring or an unsaturated bond may be included, but it is preferable that the amount is small, for example, 0 to 20% by mass in the resin or oligomer, Preferably 0-10 mass% is good. Examples of the aromatic ring contained in the resin or oligomer include a benzene ring and a naphthalene ring, and examples of the unsaturated bond include a double bond and a triple bond.

  In addition, even if the resin contains a resin as a solid or liquid fluorescent colorant, and the resin contains an unsaturated bond in an amount more than the above-mentioned amount, after fixing, the resin is cured / crosslinked. The resin in the present invention may contain a lot of unsaturated bonds as long as the unsaturated bond disappears.

  Further, when the fluorescent colorant of the present invention is an aqueous dispersion, the resin or oligomer as the resin is preferably a hydrophilic group such as a carbonyl group, a sulfonic acid group, a phosphoric acid group and / or an alkaline substance thereof. One or two or more kinds selected from Japanese salts, amino groups and neutralized salts of acidic substances thereof, and polyethylene glycol groups are contained and used by dissolving, dispersing or emulsifying in water.

  Although the usage form of resin used by this invention is not specifically limited, It can be used according to the form of each fluorescent colorant. For example, if the fluorescent colorant is in a solid form, the resin can be used as a solid or melted, and the resin is dissolved, dispersed, or emulsified in an organic solvent or water to obtain a fluorescent colorant. Thereafter, the organic solvent and water are volatilized to obtain a solid fluorescent colorant. Moreover, when it is liquid, it is used by dissolving, dispersing, and emulsifying the resin in an organic solvent or an aqueous system.

  Further, in order to impart coloring ability and recording ability, the nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, or oil as an additive in the fluorescent colorant of the present invention It is also possible to use a soluble pigment dispersant, water repellent, smoothing agent and the like in combination.

  The surfactant is a conventionally known surfactant, and is not particularly limited. For example, the surfactant is a compound, alkyl or aryl sulfonate, alkyl or aryl monoalcohol sulfate, alkyl ester phosphorus. Anionic surfactants such as acid salts, cationic surfactants such as tetraalkylammonium salts, nonionic surfactants such as polyethylene glycol monoalkyl ethers or esters and polyethylene glycol alkylphenyl ethers, amphoteric compounds such as imidazole and alkyl betaines A surfactant or the like is used.

  Further, as the oil-soluble dispersant, conventionally known ones can be used, and are not particularly limited. For example, polycaprolactone, poly12 hydroxystearic acid and polyethylenimine amidated or polyimine, which are also in the above-described resins, can be used. Compounds in which naphthalene group or nonylphenyl group is ester-bonded to the end of caprolactone or poly-12 hydroxystearic acid, commercially available products are “Bursolol” brand name “Solsperse”, Kawaken Fine ’s brand name “Hinoact” , Trade name “Disperbic 160” series manufactured by Big Chemie.

  It is desirable that the above-mentioned various additives are not colored so that the fluorescent intensity of the fluorescent pigment in the fluorescent colorant is not reduced, and further, light absorption in the ultraviolet region is desired to be as small as possible. Must have features.

  In the fluorescent colorant of the present invention, a conventionally known dispersion medium is used in accordance with each application. Examples of the dispersion medium include the resin itself, water, an organic solvent, a long-chain aliphatic hydrocarbon solvent, a hydrocarbon wax, and a monomer group having an α, β-unsaturated bond.

  The dispersion medium is for dispersing the pigment or resin or dissolving the resin to obtain a fluorescent colorant. When each of the dispersion media is used, water is used when water is used. If an organic solvent or a long-chain aliphatic hydrocarbon solvent is used, it becomes an oily fluorescent colorant, and the resin itself such as polyester resin, polyacryl resin, hydrocarbon wax is used. When used, it becomes a solid, solvent-free fluorescent colorant, and when a monomer having an α, β-unsaturated bond is used, it becomes a solvent-free ultraviolet / electron beam curable fluorescent colorant. .

  Here, in the dispersion medium, the resin is as described above, and organic solvents, long-chain aliphatic hydrocarbon solvents, hydrocarbon waxes, and monomers having α, β-unsaturated bonds are generally used. For example, the organic solvent may be an alcohol solvent such as methanol or isopropanol, an aromatic hydrocarbon solvent such as toluene or xylene, methyl ethyl ketone or methyl isobutyl. Ketone solvents such as ketones, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as tetrahydrofuran and diethylene glycol dimethyl ether, glycol solvents such as triethylene glycol monobutyl ether and propylene glycol monomethyl ether acetate, dimethylformamide and Examples thereof include amide solvents such as dimethylacetamide and sulfur solvents such as dimethyl sulfoxide.

  Examples of the long-chain aliphatic hydrocarbon solvent include isoparaffins such as isooctane and isononane, and trade names Isopars and Exols manufactured by Exxon Chemical. These solvents may be used alone, but are generally used as a mixed system of several kinds of solvents according to the purpose of use.

  The hydrocarbon wax is solid at room temperature, preferably has a melting point of 60 ° C. to 130 ° C., and has a low viscosity after melting. For example, olefin waxes such as polyethylene, polypropylene and paraffin wax, alcohol waxes such as stearyl alcohol and behenyl alcohol, carboxylic acid waxes such as stearic acid and behenic acid, stearyl stearate, methyl behenate and tristearyl glyceride And aliphatic amides such as stearic acid amide and bisethylene stearyl amide.

  Examples of the monomer having an α, β-unsaturated bond include vinyl monomers such as styrene and vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) Monofunctional acrylic monomers such as benzyl acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and polyols such as 1,4-butanediol and pentaerythritol Examples include (meth) acrylic acid esters such as polyfunctional acrylic monomers such as (meth) acrylic acid esters.

  Even in these monomers having an α, β-unsaturated bond, as in the case of the resin used, there is no coloring so that the fluorescence intensity of the fluorescent pigment in the fluorescent colorant is not decreased, and further, the ultraviolet region. It is desirable that the light absorption at is as small as possible.

  Further, conventionally known additives such as charge control agents, fluidizing agents, preservatives, antioxidants, ultraviolet absorbers, plasticizers are used according to the respective uses of the fluorescent colorant of the present invention. , Photopolymerization initiators, radical generators, sensitizers and the like are used and are not particularly limited.

  The fluorescent colorant of the present invention is a coating method using aqueous and oily coating agents and a printing method using printing inks such as letterpress ink, planographic ink, intaglio gravure ink, stencil screen ink and flexographic ink, In the image recording ink jet method, the recording method is an aqueous ink jet recording method, a solvent-based ink jet recording method, a solid heat-melt ink jet recording method, an ultraviolet curable ink type ink jet recording method, a thermal transfer method, and an electrophotographic recording agent. Can be used.

  Further, the fluorescent colorant of the present invention is a stationery colorant, a paint colorant, a printing ink colorant, a thermal transfer colorant, an electrophotographic colorant, and an inkjet ink in an aqueous, oily, or solventless system. It is also useful as a colorant and a colorant for printing agents.

  For example, as an aqueous colorant, it is used for stationery, paint, gravure ink, inkjet ink, and printing agent, but the fluorescent pigment, non-fluorescent chromatic pigment, resin and / or dispersant in the present invention, It consists of water as a dispersion medium, an aqueous solvent as needed, and other additives.

  Oily colorants are used for stationery, paints, gravure inks, offset inks and inkjet inks, but as fluorescent pigments, non-fluorescent chromatic pigments, resins and / or dispersants, and dispersion media in the present invention. It consists of organic solvents, long chain aliphatic hydrocarbon solvents, alcohol solvents and / or glycol solvents, and other additives.

  As the resin component of the printing ink or coating agent, for example, in the case of water, casein, hydroxyethyl cellulose, styrene-butadiene copolymer latex, styrene-vinyl acetate copolymer latex, polyethylene dispersion, ethylene Examples thereof include copolymer dispersions. In the case of oily, for example, cellulose acetate butyrate resin, nitrocellulose resin, polyvinyl butyral resin, phenol modified alkyd resin, amino alkyd resin, phenol resin, rosin modified phenol resin and the like can be mentioned.

  Solvent-free colorants are used for toners in electrophotography, that is, in (color) copy systems, solid hot melt ink jet recording systems, molded articles such as films and molded articles, etc. The non-fluorescent chromatic pigment, the resin and / or the dispersant, and the dispersion medium includes a resin, a hydrocarbon wax, and other additives. Among them, examples of the ultraviolet curable ink include a fluorescent colorant, a resin and / or a dispersant in the present invention, a monomer having an α, β-unsaturated bond as a dispersion medium, water or an organic solvent as necessary, and the like. Consists of additives.

  The fluorescent colorant of the present invention includes a high concentration composition. The purpose is to contain the pigment in a high concentration, and to sufficiently disperse the colored components in advance and disperse the coloring components, or toning the color to facilitate the subsequent process. The form is used in any form of solid or liquid such as coarse particles, coarse powder, fine powder, sheet shape, and small lump shape.

  The content of each component in the fluorescent colorant used in the present invention varies depending on the purpose of use. In the dispersion composition containing the fluorescent colorant at a high concentration, the content thereof is about 10% by mass to 60% by mass, preferably about 15% by mass to 40% by mass, and is most preferable depending on the purpose of use. Used in content.

  Next, the present invention will be described more specifically with reference to examples. In the text, “part” or “%” is based on mass.

Example 1 [Water-based inkjet ink]
C. I. 10 parts of Pigment Blue 22, No. 1 in Table 1. 3 fluorescent pigments, aqueous styrene-acrylic resin aqueous solution (styrene / butyl acrylate / methacrylic acid / 2-hydroxyethyl methacrylate = 10/50/20/20 potassium salt, weight average molecular weight 35 in terms of polystyrene in GPC, 000, solid content 40%) 187.5 parts, ethylene glycol 40 parts, and pure water 160 parts were mixed well to prepare a mill base. Next, the mill base was sufficiently dispersed using a horizontal media disperser, and 212.5 parts of pure water was added to the mill base to obtain a pigment dispersion having a pigment content of 20%.

  Next, 51.0 parts of ethylene glycol, 33.0 parts of glycerin, 1 part of polyoxyethylene oleate, 0.8 part of surfactant, and 15 parts of the above-mentioned styrene-acrylic resin are added to 100 parts of this dispersion. Then, 197 parts of pure water was added and stirred, and this was centrifuged (8,000 rpm, 20 minutes) to remove coarse particles, followed by filtration with a 5 μm membrane filter to obtain a black fluorescent pigment ink. It was. The ink obtained above was filled in an ink cartridge, and solid printing was performed on glossy paper for ink-jet Photolike QP (manufactured by Konica) by an ink jet printer. The hue was slightly reddish black, and emitted yellow fluorescence when irradiated with ultraviolet light using black light.

Example 2 [Oil-based inkjet ink]
C. I. Pigment Violet 19 (Dioxazine Violet) 10 parts, No. 1 in Table 1 100 parts of fluorescent pigment of No. 5 and an acrylic resin (2-ethylhexyl methacrylate / diethylaminoethyl methacrylate = 70/30, weight average molecular weight of 25,000 in terms of polystyrene in GPC) solution of Isopar G (manufactured by Exxon, solid content 40%) After mixing and stirring 75 parts and ISOPAR G492 parts, they were sufficiently dispersed using a horizontal media disperser.

  Next, 3 parts of polyethylene glycol monolauryl ether and 197 parts of Isopar G are added to 100 parts of this dispersion, and the mixture is stirred well, adjusted to ink, filtered through a 5 μm membrane filter, and black fluorescent A pigment ink was obtained. The ink obtained above was filled in an ink cartridge, and solid printing was performed on a surface-treated 50 μm PET film by an ink jet printer. Although the hue was slightly greenish black, it emitted fluorescence when irradiated with ultraviolet light using a black light.

Example 3 [Hot Melting Solid Inkjet Ink]
C. I. Pigment Green 7 (phthalocyanine green) 1.0 part, No. 1 in Table 1 5 parts of a fluorescent pigment of No. 5, 2.5 parts of poly-12-hydroxystearic acid (polystyrene equivalent weight average molecular weight of 5,500 in GPC), paraffin wax (melting point: 65 ° C., viscosity at 100 ° C .: 5.6 mPa · s) 92.5 parts were stirred while heating at 120 ° C., and dispersed with an attritor while maintaining the temperature. Subsequently, this was heated and filtered, and solid printing was performed on a 50 μm PET film that had been surface-treated in an inkjet printer. The hue was almost neutral black, and emitted fluorescence when irradiated with ultraviolet light using black light.

Example 4 [UV curable inkjet ink]
C. I. Pigment Blue 15 (copper phthalocyanine) 3 parts, No. 1 in Table 1 100 parts of fluorescent pigment No. 6, 130 parts of trimethylolpropane triacrylate, 150 parts of phenoxyethyl acrylate, 20 parts of polyamiprolactone (polymerization average 10) polyethylenimine (number average molecular weight 8,000) amidated product, The mixture was well stirred and dispersed using a horizontal media disperser.

  Next, 40 parts of this dispersion, 10 parts of urethane acrylate (product name UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.), 92 parts of ethylene oxide-added trimethylolpropane triacrylate, 100 parts of dipropylene glycol diacrylate, photoinitiator 8 parts of benzyl dimethyl ketal were mixed well and stirred, and the ink was adjusted and filtered through a 5 μm membrane filter to obtain a black fluorescent pigment ink. The ink obtained above was filled in an ink cartridge, solid-printed on a surface-treated 50 μm PET film by an inkjet printer, and then cured by a conveyor type ultraviolet irradiation device to obtain a printed matter. The hue was black and emitted strong fluorescence when irradiated with ultraviolet light using black light.

Example 5 [Water-based ink for stationery]
C. I. Pigment Blue 15 (copper phthalocyanine) 5 parts, No. 1 in Table 1 7 parts of fluorescent pigment, 308 parts of water, 80 parts of ethylene glycol, 80 parts of an aqueous solution of ammonium ion of styrene maleic acid (styrene / maleic acid ratio = 1/1, acid value 286, solid content 35%), 8 parts of aqueous ammonia Were mixed well and dispersed in a horizontal bead mill. Subsequently, 2,048 parts of water, 160 parts of the above-described resin, 176 parts of ethylene glycol, and 16 parts of 28% ammonia water were added and stirred, and then coarse particles were removed by centrifugation. The viscosity was 3.6 mPa · s, and the pH was 9.0. When this was put on a felt pen and written on plain paper, it was gray and emitted strong fluorescence when irradiated with ultraviolet light using a black light.

Example 6 [Dry pulverized toner]
C. I. 1 part of Pigment Violet 19, No. 1 in Table 1. No. 8 fluorescent pigment 30 parts, polyester resin (maleic acid / terephthalic acid / bisphenol A ethylene oxide adduct, number average molecular weight 6,000, Tg 60 ° C.) fine powder 70 parts premixed with high speed stirrer, This roll was sufficiently kneaded, cooled and finely pulverized to obtain a fine powder of a high concentration fluorescent pigment composition containing 30% of the pigment.

  Next, 11 parts of the above high-concentration fluorescent pigment composition, 3 parts of an aluminum complex salt negative charge control agent, and 86 parts of the polyester resin used above were kneaded according to a conventional method, cooled, coarsely pulverized, and then finely pulverized with a jet mill. Then, classification was performed to obtain a fine powder of 5 to 10 μm. Colloidal silica is added as a fluidizing agent, mixed with the magnetic iron powder of the carrier, copied as a fluorescent pigment electrophotographic dry developer with an electrophotographic copying machine, and bright black that emits fluorescence with black light. A print was obtained.

The fluorescent colorant of the present invention constitutes a fluorescent black colorant by mixing a chromatic fluorescent pigment and a non-fluorescent chromatic pigment, and when a conventional dye-based fluorescent pigment is used. Unlike others, it has high concealability and colorability, and is excellent in light resistance, chemical resistance, especially chlorine resistance and water resistance, so it can be stably manufactured even in the process of manufacturing colorants, Even when used as an image recording agent, it is possible to stably record a strong black or gray fluorescent image which has been impossible in the past for a long period of time.

Claims (8)

  A fluorescent colorant comprising a chromatic fluorescent pigment, a non-fluorescent chromatic pigment, and a resin, and having a black hue. The fluorescent colorant according to claim 1, wherein the chromatic fluorescent pigment is represented by the following general formula (1).

  The fluorescent colorant according to claim 1, wherein the particle size of the chromatic fluorescent pigment is 0.03 to 10.0 µm.   The fluorescent colorant according to claim 1, wherein the blending mass ratio of the chromatic fluorescent pigment (A) and the non-fluorescent chromatic pigment (B) is 1: 1 to 50: 1.   Resin is poly (meth) acrylic resin, polyvinyl resin, polymaleic acid resin, polyester resin, polyether resin, polyurethane resin, polyamide resin, polyepoxy resin, polycarbonate resin, polysiloxane resin 2. The fluorescent colorant according to claim 1, which is a resin and / or oligomer selected from a polyolefin resin and a polyfunctional unsaturated bond-containing oligomer (ultraviolet / electron beam curable monomer).   The fluorescent colorant according to claim 1, which is a colorant for stationery, a colorant for paint, a colorant for printing ink, a colorant for thermal transfer, a colorant for electrophotography, a colorant for inkjet ink or a colorant for printing agent. .   A recording method, wherein information is recorded by a coating method, a printing method, an ink jet method, a thermal transfer method or an electrophotographic method using the fluorescent colorant according to claim 1. A recorded matter obtained by the recording method according to claim 7.